EP1647352B1 - Solder material - Google Patents

Description

The invention relates to a solder material based on tin or tin alloys for producing a solder joint between two parts of substrate metals made of iron, nickel, copper, silver or their alloys.

Known alloys for soft soldering are described in DIN EN 29453 and in EN 61190-1-3. These soft solder alloys have a melting point which is usually far below the metallic parts to be soldered. In soft soldering, the contact of the molten solder with the substrate metal causes alloying and the formation of intermetallic phases, with diffusion processes playing an essential role. The alloy formation of solder and substrate metal leads to the so-called Ablegieren the substrate metal at the Lotstelle. Especially with thin substrate metal layers, this leads to undesirable changes and losses in the functionality of these layers or of the solder joint. Although previously known lead-containing soft solders achieve good solder joints at low rates of ablation, due to the toxicity of lead these soft solders are increasingly being replaced by lead-free soft solders. When using lead-free solders, however, the effect of Ablegierens is much greater than lead-based solders. This depends on the one hand with the higher process temperatures, but also with increased process times necessary to achieve equally good wetting results of the lead-free solder on the substrate metals. Furthermore, the high tin content lead-free solder is far more aggressive than the known lead-containing solder. For example, pure tin, copper dissolves at the same temperatures about four times as fast as conventional tin-lead. Such high dissolution speeds mean that machine parts or materials with solder joints using such a soft solder are much more likely to be damaged or even lose their function. Typically, solder solders are used to braze and coat metallic parts of copper and copper alloys, nickel and nickel alloys, iron and iron alloys, and silver alloys.

In the past, therefore, many attempts have been made to improve lead-free solders by increasing the concentration of such alloying elements in soft solder as are present in the substrate metal, such as copper. From the installation technique, the use of a soft solder from a Sn97Cu3 alloy for copper pipes is known. This hypereutectic alloy accordingly contains copper in an increased concentration in the tin solder, thereby achieving a reduction in the rate of copper alloying out of the copper tube. However, this only works with correspondingly high soldering temperatures. Such conditions are for other joining processes, e.g. in electronics, not applicable.

From the patent US 5,527,628 is a lead-free solder of a eutectic tin-silver-copper alloy, optionally known with proportions of bismuth and zinc, which can also be used for electronic component connections. Likewise, a lead-free tin-silver-copper alloy, in this case containing proportions of antimony, is disclosed in the patent JP 3027441 described, which is used together with a flux as a solder paste for connection of electronic components application.

From the patent US 5,837,191 is a lead-free solder known from a tin-antimony-silver-copper alloy for use in fittings and pipe joints. By the proportions of antimony in the lead-free alloy higher strengths are possible.

Furthermore, in the American patent application US 2004/0141873 A1 discloses a soft solder composed of a tin-silver alloy having cobalt and iron contents. These two alloying elements cobalt and iron thereby reduce the aggressiveness of the tin to the iron of the contact surfaces of the iron parts to be soldered, the solder pot or stirrers or heating coils, which are made of this material and used in the soldering process. The corrosion of these iron parts increases the melting range of the soft solder, which in turn leads to a higher rate of alloying. However, only the application of the alloy for components made of ferrous materials is shown.

In electronics soldered switching assemblies are exposed to temperature changes in the switching operations. For this, the solder joints must have sufficient thermal fatigue strength. If this is not the case, coarsening of the microstructure of the soldering material at the soldering point occurs and possibly cracking which releases the electrical contact at the soldering point. The coarser and more ductile the solder material is, the sooner the circuit will fail.

From the document EP 0 847 829 A1 For example, a lead-free solder made from a tin-silver-copper alloy containing an addition of nickel is known, whereby finely divided SnNi intermetallic compounds are formed. These fine SnNi grains can better withstand temperature changes. However, the proportions of nickel also affect the melting range of the solder, so due to the relatively high levels of nickel, the melting range is increased, resulting in a larger Ablegierungsrate.

The object of the invention is therefore to provide an improved solder material for the joining technique in electronics, which leads to a lower Ablegierungsrate in the application. This object is achieved with a solder material having the features of claim 1.

• 0,001 bis 0,05 Gew% Eisen und 0,001 bis 0,15 Gew% Nickel oder
• 0,001 bis 0,05 Gew% Eisen und 0,001 bis 0,15 Gew% Kobalt oder
• 0,001 bis 0,2 Gew% Kobalt und 0,001 bis 0,05 Gew% Nickel.

The parts to be coated and soldered are usually made of the following substrate metals: copper and copper alloy, nickel and nickel alloy, iron and iron alloy, and silver alloys. Prerequisite for the solderability of these substrate metals is a good wettability of the metallic surfaces of the parts with the molten solder material. For the solder material according to the invention, tin, a tin-silver alloy, a tin-copper alloy, a tin-silver-copper alloy or one of the abovementioned base materials with proportions by weight of antimony are used as the base. Such a solder preform, hereinafter referred to as a base alloy, is added with alloy components which undergo intermetallic compounds with the substrate metal and are not yet present in the base alloy. This results in the application of the resulting soft solder material that Ablegierungsreaktionen be pushed back. In addition, it was found that due to the infinite miscibility of the elements, iron, cobalt and Nickel among themselves, these metals can also be used together in the solder, where adds the effect of each element. On the other hand, it is also possible to provide only one of these elements with a correspondingly greater proportion by weight in the soft solder alloy. In the tin-lead solders used earlier, the proportions of these elements, iron, nickel, cobalt, were always kept as low as possible. These elements were considered undesirable contaminants that interfere with the brazing process. When these elements are added to the abovementioned base alloys, however, a total weight fraction of up to 1% by weight is not critical. However, additions of up to a total of 0.25% by weight are preferred. Particularly preferred are solder alloys with:

• 0.001 to 0.05% by weight of iron and 0.001 to 0.15% by weight of nickel or
• 0.001 to 0.05% by weight of iron and 0.001 to 0.15% by weight of cobalt or
• 0.001 to 0.2% by weight of cobalt and 0.001 to 0.05% by weight of nickel.

This metered addition of iron, cobalt and / or nickel has the effect of reducing the rates of depletion. However, these dosages have no effect on the physical properties of the solder, i. the density, the melting point and the crystal structure remain unchanged. Likewise, the wettability of the soft solder is not affected. It results in the coating of the parts to be soldered, a uniform surface on the substrate metals.

In addition, the alloying of alloying metals from the group of rare earths, such as, for example, cerium, lanthanum or neodymium, results in grain refinement of the soft solder. This grain refinement becomes visible in the uniform appearance of the metallic surface of the coating and the surfaces of the solder joints. As a result of this finer microstructure, recrystallization processes or material coarsening are delayed by thermal influence in the solder joint. This advantageously allows the use of the solder material according to the invention as a microdosed solder for soft soldering tasks in electronics, electrical engineering and precision engineering and this under, compared to the prior art, same and even more favorable conditions.

In a preferred embodiment, the addition of rare earth is carried out via a so-called mischmetal. This is understood to mean an alloy containing cerium, lanthanum and neodymium as main constituents and about 3% by weight of iron. A commercial mixed metal contains, in addition to the 3% by weight of iron, 45% by weight of cerium, 45% by weight of lanthanum and 5% by weight of neodymium. The rest are unavoidable impurities. This mischmetal is added in proportions by weight of 0.001 to 0.05% by weight, preferably together with 0.001 to 0.1% by weight of cobalt, of one of the abovementioned base alloys.

• Eisen zu Nickel 1:1 1 bis 1:3
• Eisen zu Kobalt 1:1 bis 1:4
• Kobalt zu Nickel 1:1 bis 5:1
• Mischmetall zu Kobalt 1:1 bis 1:4.

Various studies have shown that the following weight ratios are advantageous in the solder material, namely:

• Iron to nickel 1: 1 1 to 1: 3
• Iron to cobalt 1: 1 to 1: 4
• Cobalt to nickel 1: 1 to 5: 1
• Mixture to cobalt 1: 1 to 1: 4.

For soldering tasks in the electronics industry, where silver metallizations and similar can be found on the component surfaces. with platinum and / or palladium shares, an additional alloying of palladium and / or platinum in proportions by weight of 0.001 to 0.1% by weight to one of the aforementioned soft solder alloys has proven to be favorable.

• Sn Cu 0,7 Ce 0,03 Co 0,08 Ni 0,02 Pd 0,004 (Lotbad)
• Sn Ag 3,7 Cu 0,6 La 0,04 Fe 0,02 Ni 0,04 Pt 0,005 (Lotpaste)
• Sn Ag 3,6 Cu 0,6 La 0,04 Fe 0,01 Co 0,04 Pd 0,01 (Lotpaste)
• Sn Ag 3,5 MM* 0,05 Co 0,08 Pd 0,005 (Lotpaste)
  *) Mischmetall.

In the following, proven design variants of soldering agents are listed which have led to permanently reliable solder joints. These solder baths or solder pastes contain inventive solder materials of the composition:

• Sn Cu 0.7 Ce 0.03 Co 0.08 Ni 0.02 Pd 0.004 (solder bath)
• Sn Ag 3.7 Cu 0.6 La 0.04 Fe 0.02 Ni 0.04 Pt 0.005 (solder paste)
• Sn Ag 3.6 Cu 0.6 La 0.04 Fe 0.01 Co 0.04 Pd 0.01 (solder paste)
• Sn Ag 3.5 MM * 0.05 Co 0.08 Pd 0.005 (solder paste)
  *) Mischmetal.

In addition, the alloy Sn Cu3 Ce 0.01 Co 0.1 Ni 0.1 has proven to be well suited for high temperature applications.

Further variants of soldering agents additionally contain 0.001 to 0.01% by weight of phosphorus, which serves as a deoxidizer.

The solder materials according to the invention can be present in the form of bars, rods or powder in order to produce, for example, a solder bath. The solder materials can also be used to produce solid or flux-filled wires. For special applications, these solder materials can be produced in the form of a film or as a molded part. An application of the solder material according to the invention as solder paste is also possible. Under these conditions, solder joints for parts of substrate metals, such as iron, nickel, copper or their alloys and silver alloys can be prepared in which the metallic surfaces of the substrate metals are coated with the solder material. Such metallic surfaces may be surfaces of printed circuit boards, metallic pads on electrical, electronic or mechanically functional components as well as other contact surfaces. Also, solder joints can be made if the pieces of substrate metal are wires, strands, eyelets, or lugs.

Embodiment:

The preparation of the solder material can be done in various ways, namely from the pure metals or with the aid of master alloys.

There are few problems to produce tin-silver, tin-copper or tin-silver-copper alloys from pure metals on a production scale, because the solubility of small amounts of silver and / or copper in pure tin at temperatures up to 400 ° is already relatively high , However, this is different if one wants to add iron, cobalt, nickel or elements of the rare earth whose dissolution rate in a tin melt is relatively low. For acceptable dissolution rates, significantly higher temperatures are needed. Therefore, master alloys are favorably used in the production of the solder alloys according to the invention.

• Sn 99,8 Fe 0,2
• Sn 99,2 Co 0,8
• Sn 99,2 Ni 0,8
• Sn 99,7 Ce 0,3.

From the pure metals (99.9% by weight) iron, cobalt, nickel and cerium, the following master alloys were separately prepared with pure tin at about 800 °:

• Sn 99.8 Fe 0.2
• Sn 99.2 Co 0.8
• Sn 99.2 Ni 0.8
• Sn 99.7 Ce 0.3.

Higher contents of the alloy components have proved unfavorable, because there is a risk that the forming intermetallic phases separate too much during cooling and solidification. These so-called. Seigerungen then lead to inhomogeneities in the master alloy. The master alloys are poured for further use in triangular bars or flat bars. These triangular or flat bars are suitable shapes to make accurate dosages for the target alloys.

By way of example, the production of 1000 kg of a SnCu soldering material is subsequently produced:
First, the base alloy of 899.13 kg tin and 6.50 kg copper is prepared as usual. Then be 28.13 kg Sn 99.2 Ni 0.8 alloy 56.25 kg Sn 99.2 Co 0.8 alloy and 10.00 kg Sn 99.7 Ce 0.3 alloy added, melted and tempered to 500 °. After a half-hour rest, the mixture is stirred and the melt is cooled to 430 °. After removing the resulting ash, the sample is taken for analysis and pouring into 1kg bars.

The analysis of the above approach by means of a radio spectrometer showed the following composition in% by weight: Cu: 0.62 Pb: 0.031 Ag: 0.0061 sb: 0,017 Co: 0.048 Au: <0.001 Ni: 0.026 al: <0.001 Ce: 0,003 CD: <0.001 Fe: 0,018 Zn: <0.001 Bi: 0.0075 As: 0.0052 In: 0.0024 Sn: rest

The preparation of other alloys according to the invention can be carried out in an analogous manner.

Ablegierungsversuche:

Lead-free solder alloys have higher rates of depletion than leaded solders due to their high tin content and higher working temperatures during soldering. The alloying is especially important when soldering thin layers in electronics. The most commonly used material for printed conductors on printed circuit boards is copper. The decalcifying of the copper means a change in the solder joint caused by the reaction between tin and copper. In addition to the substrates to be soldered and soldering tools that come into contact with the hot solder, attacked by the tin-containing alloys. The consequences are pitting and ultimately the destruction of the equipment.

Ablegierungsversuche with solder material according to the invention were made on copper and nickel substrate metals. For this purpose, the copper or nickel material was immersed in the liquid solder at high temperature. So that the solder wets the material well, a flux was used.

Table 1 shows deposition rates of known solders (Nos. 1 to 6) and solders according to the invention (Nos. 7 to 12), wherein in each case one solder of the same base alloy was used for comparison for a solder according to the invention.

The considerably lower rates of ablation for Nos. 7 to 12 are clear in comparison to Nos. 1 to 6.

The largest difference can be found in the tin-silver-copper alloys (Nos. 8, 9 and No. 2, 3). The alloying at higher temperatures (400 ° C) is much higher, but again shows the beneficial reduction of the alloy at No. 12 compared to No. 6. <u> Table 1: Comparison of Alloy Rates: </ u> No. solder alloys Ablation rates in μm / s delay factor temperature 1. Sn 96 Ag 4 0.57 1 300 ° C Second Sn 96.5 Ag 3.0 Cu 0.5 0.67 1 300 ° C Third Su 95 Ag 3.8 Cu 0.7 0.39 1 300 ° C 4th Su 99 Cu 0.7 0.35 1 300 ° C 5th Su 97 Cu 0.3 0.14 1 300 ° C 6th Sn 97 Cu 0.3 1.15 1 400 ° C 7th Su 96 Ag 4 Co 0.045 Ni 0.02 Ce 0.003 0.28 2.03 300 ° C 8th. Su 96.5 Ag 3.0 Cu 0.5 Co 0.045 Ni 0.02 Ce 0.003 0.23 2.85 300 ° C 9th Sn 95 Ag 3.8 Cu 0.7 Co 0.045 Ni 0.02 Ce 0.003 0.12 3.25 300 ° C 10th Sn 99 Cu 0.7 Co 0.045 Ni 0.02 Ce 0.003 0.18 1.96 300 ° C 11th Sn 97 Cu 0.3 Co 0.045 Ni 0.02 Ce 0.003 0.05 3.00 300 ° C 12th Sn 97 Cu 0.3 Co 0.045 Ni 0.02 Ce 0.003 0.51 2.25 400 ° C

The Ablegierungsrate of copper is about half as large in the solders used according to the invention, as in the comparable known solders. Therefore, it is possible to solder even with lead-free alloys thin layers or thin cables.

Nickel deposition could not be determined using the same method since the rates of alloying were below 10 μm / hour.

The solder materials of the invention show drastically reduced Ablegierungsraten compared to known lead-free solders, so that dissolve metallization on components and circuit boards not so fast and the life of the soldering is extended.

Claims (17)

1. Soldering material with low rates of dissolution to establish a solder connection for electrical and/or electronic components, whereby, the soldering material features a compound of 0.2 to 5% weight silver and/or copper, 0.001 to 0.25% weight cobalt or a minimum of two elements selected from the group iron, cobalt, nickel, 0.001 to 0.5% weight of a component selected from the group of the seldom earths no or 0.001 to 0.1 % weight palladium or platinum, no or 0.001 to 0.01% weight phosphorous, rest tin and usual contamination
2. Soldering material according to claim 1, characterized in that the soldering material contains 0.001 to 0.05% weight of iron and 0.001 to 0.15% weight of nickel.
3. Soldering material according to claim 2, characterized in that the soldering material contains iron and nickel in a ratio of 1:1 to 1:3.
4. Soldering material according to claim 1, characterized in that the soldering material contains 0.001 to 0.05% weight of iron and 0.001 to 0.15% weight of cobalt.
5. Soldering material according to claim 4, characterized in that the soldering material contains iron and cobalt in a ratio of 1:1 to 1:4.
6. Soldering material according to claim 1, characterized in that the soldering material contains 0.001 to 0.2% weight of cobalt and 0.001 to 0.05% weight of nickel.
7. Soldering material according to claim 6, characterized in that the soldering material contains cobalt and nickel in a ratio of 1:1 to 5:1.
8. Soldering material according to claim 1, characterized in that the soldering material contains 0.001 to 0.2% weight of cobalt.
9. Soldering material according to claims 1 to 8, characterized in that the soldering material contains 0.001 to 0.05% weight of a minimum of one alloying components selected from the group of seldom earths preferably cerium and/or lanthanum and/or neodymium.
10. Soldering material according to claims 1 to 9, characterized in that it is present in the form of ingots or rods or a powder or as solid wire or as wire filled with liquid or as film or as a formed part or as soldering paste.
11. Using the soldering material according to one of the claims 1 to 10 for solder connection between two parts of the same or different substrate metals, contained as the main components iron or nickel or copper.
12. Using the soldering material according to claim 1 with palladium or platinum as a solder connection two parts made from substrate metals containing silver.
13. Using the soldering material according to one of the claims 1 to 10 for solder connections characterized in that the parts made from substrate metal are metallic surfaces on printed circuit boards or metallic connection surfaces on electrical, electronic and mechanical functional components or other contact surfaces.
14. Using the soldering material according to one of the claims 1 to 10 for solder connections characterized in that the parts made from substrate metal are wires, strands, terminal lugs or cable shoes.
15. Procedure to establish a solder connection according to claim 1, characterized in that the basis for the soldering material is inserted in tin or tin alloy and alloying components are added in the form of metals or composition metals, up to a compound of: 0.2 to 5% weight silver and/or copper, 0.001 to 0.25% weight cobalt or a minimum of two elements selected from the group iron, cobalt, nickel, 0.001 to 0.5% weight of a component selected from the group of the seldom earths no or 0.001 to 0.1 % weight palladium or platinum, no or 0.001 to 0.01% weight phosphorous, rest tin and usual contamination.
16. Procedure according to claim 15, characterized in that the seldom earths are added in the form of composition metal, preferably 0.001 to 0.05% weight of composition metal, whereby, composition metal is an alloy of 3% weight iron and 45% weight cerium and 45% weight lanthanum and 5% weight neodymium and the rest other seldom earths and unavoidable contamination.
17. Procedure according to claim 16, characterized in that 0.001 to 0.1 % weight cobalt is added and a ratio of composition metal to cobalt is set at from 1:1 to 1:4.